Basic Balances on Reactive

Processes
Academic Resource Center
 Motivation
• This topic was chosen because it is believed to
be one of the core principles of chemical
processes
• Students would first need to learn this
foundation of process balances before building
more specific skills
 Introduction
• The knowledge of writing balances on reactive
processes can be applied in many places:
power plants, pharmaceutical plants, etc
• Usually, one would first need to draw a
flowchart depicting the various processes
• Then, for most of the course, students will
need to calculate the flow rates and
compositions of all the flows in the flowchart
 The General Balance Equation
Accumulation = In – Out + Generation - Consumption

• Accumulation: buildup within system

• In: enters through system boundaries
• Out: leaves through system boundaries
• Generation: produced within system
• Consumption: consumed within system
 The Idea of Control Volume
Process
min (kg CH4) Unit mout (kg CH4)

• The irregular shape may represent any process unit

(evaporator, reactor, condenser, etc.)
• We draw a rectangle around the unit to represent the
desired control volume
• Then, the general balance equation is applied to this
control volume
– Whatever that is entering the rectangle is the “In”
– Whatever that is exiting the rectangle is the “Out”
– Whatever that is being produced/consumed in the rectangle is
the “Generation/Consumption”
– Whatever that remains in the rectangle is the “Accumulation”
 Three Different Balances
Three different balances may be written to
determine an unknown flow rate for a reactive
process:
a) Molecular Species Balances
b) Atomic Species Balances
c) Extent of Reaction
 Example 1
• Let us consider the dehydrogenation of
ethane:
C2 H 6  C2 H 4  H 2

• Assuming 100 kmol/min of ethane is fed to the

reactor and the molar flow rate of hydrogen in
the product stream is 40 kmol/min
 Solution to Example 1
• Since most analyses would be done at steady-
state (accumulation = 0), the general balance
equation is reduced to the following:
In + Generation = Out + Consumption
• This example will now be solved using the
three different balances introduced earlier:
a) Molecular Species Balances
b) Atomic Species Balances
c) Extent of Reaction
 1a) Molecular Species Balances
• Usually used when a reaction is involved
• Thus, there should be some species that are
being generated and some other species that
are being consumed
• Once a generation/consumption term has
been calculated, the other terms can be
calculated directly from stoichiometric
equation
 1a) Molecular Species Balances
Process
100 kmol C2H6/min 40 kmol H2/min
Unit
n1 (kmol C2H6/min)
C2 H 6  C2 H 4  H 2 n 2 (kmol C2H4/min)

• H2: generation = output

GenH 2 (kmol H 2 generated / min)  40 kmol H 2 / min

• C2H6: input = output + consumption

40 kmol H 2 generated  1 kmol C2 H 6 consumed 
100  n1    n1  60 kmol C2 H 6 / min
min  1 kmol H 2 generated 
• C2H4: generation = output
40 kmol H 2 generated  1 kmol C2 H 4 generated  n2  40 kmol C2 H 4 / min
   n2
min  1 kmol H 2 generated 
 1b) Atomic Species Balances
• Usually leads to most straightforward solution
procedure, especially when more than one
reaction is involved
• Since atomic species can neither be generated
nor consumed, all atomic balances take the
form of “input = output”
 1b) Atomic Species Balances
Process
100 kmol C2H6/min 40 kmol H2/min
Unit
n1 (kmol C2H6/min)
C2 H 6  C2 H 4  H 2 n 2 (kmol C2H4/min)

• C:
100 kmol C2 H 6  2 kmol C  n1 kmol C2 H 6  2 kmol C  n2 kmol C2 H 4  2 kmol C 
       
min  1 kmol C2 H 6  min  1 kmol C2 H 6  min  1 kmol C2 H 4 
100  n1  n2

• H:
100(6)  40(2)  n1 (6)  n2 (4)
520  6n1  4n2
• Solving simultaneously gives
n1  60 kmol C2 H 6 / min n2  40 kmol C2 H 4 / min
 1c) Extent of Reaction
• As for the molecular species balances, this
method is usually used when a reaction is
involved
• However, this method tends to be more useful
when there are multiple reactions
• Recall: n  
n   
i i0 i
– ν is the stoichiometric coefficient
• Reactants: -ve Products: +ve
– ξ is the extent of reaction
 1c) Extent of Reaction
Process
100 kmol C2H6/min 40 kmol H2/min
Unit
n1 (kmol C2H6/min)
C2 H 6  C2 H 4  H 2 n 2 (kmol C2H4/min)

• H2(ν=1): 40 kmol H 2 / min  0  1( )   40 kmol / min

• C2H6(ν=-1): n1  100  (1)  100  40  60

n1  60 kmol C2 H 6 / min

• C2H4(ν=1): n2  0  1( )  40

n2  40 kmol C2 H 4 / min
 Example 2
• Dehydrogenation of Propane
C3 H 8  C3 H 6  H 2
• The process is to be designed for a 95% overall
conversion of propane. The reaction products are
separated into two streams:
– the first, which contains H2, C3H6, and 0.555% of the
propane that leaves the reactor, is taken off as product;
– the second stream, which contains the balance of the
unreacted propane and 5% of the propylene in the first
stream, is recycled to the reactor.
• Calculate the composition of the product, the ratio
(moles recycled)/(mole fresh feed), and the single-pass
conversion
 Solution to Example 2
Fresh feed
100 mol C3H8 Product
n1 mol C3H8
Reactor n3 mol C3H8
Separator n6 mol C3H8
n2 mol C3H6 n4 mol C3H6 n7 mol C3H6
Recycle n5 mol H2 n8 mol H2
n9 mol C3H8
n10 mol C3H6

• Basis: 100 mol fresh feed

• Product composition: n6/(n6+n7+n8)
• Recycle ratio: (n9+n10)/100
• Single-pass conversion: 100%*(n1-n3)/n1
• Need: n1, n3, n6, n7, n8, n9, n10
 Example 2: Discussion
• This time we have multiple units and a mixing
point, therefore, we can draw a control volume
around each unit, mixing point, and around
the overall process
• “…95% overall conversion of propane.”
n6 = 0.05*100 = 5 mol C3H8

• “…0.555% of propane that leaves the reactor,”

– n6 = 0.00555*n3 -> n3 = 5/0.00555 = 900 mol C3H8

• “…5% of the propylene in the first stream,”

– n10 = 0.05*n7 -> to be solved later
 2 a) Molecular Species Balances
Overall system
• C3H6: generation = out
95 mol C3 H 8 consumed  1 mol C3 H 6 generated 
   n7
min  1 mol C3 H 8 consumed  n7 = 95 mol C3H6

• H2: generation = out

95 mol C3 H 8 consumed  1 mol H 2 generated 
   n8 n8 = 95 mol H2
min  1 mol C3 H 8 consumed 

n6 = 5 mol C3H8 2.6 mol% C3H8

n7 = 95 mol C3H6 48.7 mol% C3H6
n8 = 95 mol H2 48.7 mol% H2
 2 a) Molecular Species Balances
Separator: In = Out (no reaction)
• C3H8
– n3 = n6+n9 -> n9 = n3-n6 = 900-5 = 895 mol C3H8

• C3H6
– Recall: n10 = 0.05*n7 -> n10 = 0.05*95 = 4.75 mol C3H6

– n4 = n7 + n10 -> n4 = 95+4.75=99.75 mol C3H6

– Border is dashed because we did not need n4

• H2
– n5 = n8 n5 = 95 mol H2
 2 a) Molecular Species Balances
Mixing Point: In = Out (no reaction)
• C3H8
– 100+n9 = n1 -> n1 = 100+895 = 995 mol C3H8

• C3H6
– n10 = n2 -> n2 = 4.75 mol C3H6

• Recycle ratio = (n9+n10)/100 9.00

mol recycle
mol fresh feed
• Single-pass conversion = 100%*(n1-n3)/n1
9.6%
 2 b) Atomic Species Balances
Overall System: In = Out
• C:
100(3)  n6 (3)  n7 (3)  5(3)  n7 (3) n7 = 95 mol C3H6

• H:
100(8)  n6 (8)  n7 (6)  n8 (2)  5(8)  95(6)  n8 (2) n8 = 95 mol H2

• Product composition:
n6 = 5 mol C3H8 2.6 mol% C3H8
n7 = 95 mol C3H6 48.7 mol% C3H6
n8 = 95 mol H2 48.7 mol% H2
 2 b) Atomic Species Balances
Separator: In = Out
• Recall: n10 = 0.05*n7 -> n10 = 0.05*95 = 4.75 mol C3H6

• C: n (3)  n (3)  n (3)  n (3)  n (3)  n (3)

3 4 6 7 9 10

900(3)  n4 (3)  5(3)  95(3)  n9 (3)  4.75(3) [1]

• H: n3 (8)  n4 (6)  n5 (2)  n6 (8)  n7 (6)  n8 (2)  n9 (8)  n10 (6)

900(8)  n4 (6)  n5 (2)  5(8)  95(6)  95(2)  n9 (8)  4.75(6) [2]

• We have 2 equations and 3 unknowns (n4, n5, n10)

• Since we know that no H2 is recycled, n5 = n8,
thus, the unknowns can be found by solving the
equations simultaneously
n5 = 95 mol H2 n4 = 99.75 mol C3H6 n9 = 895 mol C3H8
 2 b) Atomic Species Balances
Mixing Point: In = Out
• C:
100(3)  n9 (3)  n10 (3)  n1 (3)  n2 (3)
300  895(3)  4.75(3)  n1 (3)  n2 (3) [3]
• H: 100(8)  n9 (8)  n10 (6)  n1 (8)  n2 (6)
800  895(8)  4.75(6)  n1 (8)  n2 (6) [4]

• Now, we have 2 equations and 2 unknowns (n1,

n2) n = 4.75 mol C H
2 n = 100+895 = 995 mol C H
3 6 1 3 8

mol recycle
• Recycle ratio = (n9+n10)/100 9.00
mol fresh feed
• Single-pass conversion = 100%*(n1-n3)/n1
9.6%
 Example 2: Further Discussion
• As can be seen above, the problem can be solved
simply by analyzing only the overall system, separator,
and mixing point
• Furthermore, since these units do not involve reactions,
the extent of reaction method does not apply
• Also, for the separating and mixing sections, the
molecular species balances method leads to simpler
calculations as compared to the atomic species
balances method
• It is also worthy to note here that you can use different
methods at different points
– E.g. It may be easier to solve the overall system balance
using atomic species balances, then use molecular species
balances to solve for the other points
 Problem 1
• Incomplete Combustion of Methane
– Methane is burned with air in a continuous steady-
state combustion reactor to yield a mixture of carbon
monoxide, carbon dioxide, and water. The reactions
taking place are
3
CH 4  O2  CO  2 H 2O (1)
2
CH 4  2O2  CO2  2 H 2O (2)
– The feed to the reactor contains 7.80 mole% CH4,
19.4% O2, and 72.8% N2. The percentage conversion of
methane is 90.0%, and the gas leaving the reactor
contains 8 mol CO2/mol CO. Calculate the molar
composition of the product stream.
 Hints

nCH4 mol CH4

nCO mol CO
100 mol Process nCO2 mol CO2
0.078 mol CH4/mol Unit nH2O mol H2O
0.194 mol O2/mol nO2 mol O2
0.728 mol N2/mol nN2 mol N2

• Basis = 100 mol Feed

 Problem 2
• The reaction between ethylene and hydrogen
bromide to form ethyl bromide is carried out in
a continuous reactor. The product stream is
analyzed and found to contain 51.7 mole%
C2H5Br and 17.3% HBr. The feed to the reactor
contains only ethylene and hydrogen bromide.
• If the molar flow rate of the feed stream is 165
mol/s, what is the extend of reaction?
 Problem 3
• Methane and oxygen react in the presence of a
catalyst to form formaldehyde. In a parallel
reaction, methane is oxidized to carbon dioxide
and water:
CH 4  O2  HCHO  H 2O
CH 4  2O2  CO2  2 H 2O
• The feed to the reactor contains equimolar
amounts of methane and oxygen. Assume a basis
of 100 mol feed/s. The fractional conversion of
methane is 0.9. and the fractional yield of
formaldehyde is 0.855.
• Calculate the two extents of reaction and the
molar composition of the reactor output stream.
 References
• Felder, Richard M. Elementary principles of
chemical processes. New York: John Wiley,
1999. Print.